Monosubstituted desoxyglycoses and process for preparing the same



Patented June 7, 1949 omreo P93 "No Drawing. Application December 31; 1945, Serial N0. 638,585-

12- 'Claims.- (01. zen-"333) This invention'relates t a new classoforganic mm chemical compounds More" particularly it H relatestomonosiibstituted desoxyglyooses wherel I, in the sulostituent group imay bealkyl; aryl or H aralkyl and is attaclied to -th'e carbon atom of 5 note. the gly'cose -ske1eton, -it be'iiig iim'iers'tood that in H0 0A0 aldoses the number one carbon atom refers to How the reducinggroup" of -reducing end of the molecule, and tc'the'proeess'bf "preparing suchdescxy 1320A glycoses. For convenience 6:: reference herein 1 Furth r exampleslof t e products of. our inventhese 'monosubstitiitd'" deso y lyflo es b r tion include the" alpha and beta isomers of: ferred to hereinafter as- I-RJ-dsoxy'glycoses, it i a v a v t r p-(Tetraacetyl-D-glucopyranosy1) toluene 2fi$fi$fif represents an alkyl p-(D-gllzucclipyranosyl)toluene or 1-p-'to1y1-1-des- I oxy'e -g ucose" 53;? g fii ggigfiyggg be repre' p-(Tetraacetyl-D glucopyranosyl) naphthalene p-(D glucopyranosylnaphthalene) R a 1 (Tetraacetyl-D!g1ucopyranosyl) butane I 1-butyld-desoxyrD glucose TriacetyLD:xylopyranosylbenzene I I l-phenyl 1=' desoxy-D xylose' p- (Triacetyl-Dmylopyranosyl) toluene 6320B p- (D xylopyranosyl)toluene- Heptaacetyllactopyranosylbenzene- Lactopyranos'ylb'enzene" Arylde'soxyglycoses" maybe prepared b'yhringing about the reaction between certain carbohydrate derivativesandi. an aromatic hydrocarbon in the presence of aluminum chloride. Such a process of making; suc'liicompoiinds is disclosed wherein R may be either-an alkyl, ary1,-or aralkyl group and n is a whole-number, usually 3on4;

A specific example of a l-Ri -l desoxyglycose'obtained by the process of thepresent'invention is beta D glucopyranosylben'zene. An alternate name for this compound'is "L-phenyI-I-deSoXygluwse' structural r thls andeclaimeclin co pndihg. application Serial No. pound may be representecl -as follows: 638,583; filed December 1945 0 However, the yields of such compounds obtained by practice of 'this method are not as "high as might bedes'ired'and the isolation of the prod- OH "ucts is somewhat complicated. not mi 0 An object ofthe resent invention is toproh vide a new sen s o eompounds; i.'ve., l-R-l-clesoxyglycoses. A'fiirther ohject"is"'to'provide an effi'c'ient' process fer the preparat'ion'thereof-in cmoir substantial yields.

These objects area'cc'omplished by bringing about thereaction b'etwe'en a suitable Grignard reagent and a poli acylglycos'yl"halide or polyacylglycosyl" ester or 1 equivalent" and the like.

Several attempts toiefi'ect the reaction between suchcarbohydrate derivatives-endGrignard re- A specific example of a derivative'ofa l-R-ldesoxygly'coseobtain ed b'ythe" process of the present 'invention' istetrMcetyhbeta-D gluco-- pyranosylbenz'ene. "Ifwo alternate names are 1- phenyl 1 desoxy 2",3',4;6-' tetraacetylbeta- D-slucose and 2;3,4l6-te'traecefiy1-Pphenylelfi agents have beenreco'idedLin thei'literature; but a hyd e structura formula theseh'ave'b'eenfailures (P aalar'id' Hornstein, thereformayibe' r'ep'reseiitaasrcnowsz- Ber., 39; 1361','2'823' ('1906)' {Fischer andI-Iess, ib'ioL,

45, 912 (1912); Friischl, Zellner and Zak, Monatslm, 55, 25 (1930)). In contrast to the negative results of previous workers, the present invention provides a means for bringing about the interaction of Grignard reagents and polyacylglycosyl halides or polyacylglycosyl acetate or equivalent carbohydrate and the like.

The reaction between carbohydrate derivatives such as above specified and a Grignard reagent is believed to proceed according to the following illustrative equation involving the use, in this instance, of a polyacetylglucosyl derivative:

wherein B. may be an alkyl, aryl or aralkyl group; X represents a halogen atom, and Y represents a halide or acyloxy radical.

Hydrolysis of the reaction products produces (EHzOH a monosubstituted desoxyglycose and CHeCRzOH, a tertiary alcohol.

In carrying out the present invention there may be used any glycosyl halide or ester having protected hydroxyl groups. Polyacylglycosyl halides are particularly satisfactory. Among these which may be used are 2,3,4,6-tetraacetylglucosyl chloride, 2,3,4-triacetylxylosyl chloride, heptaac'etyllactosyl chloride. Polyacylglycoses, such as glucose pentaacetate, may also be used. In fact there may be used any carbohydrate derivative containing an aldehydic or ketonic function, the carbon atom of which has attached to it a group Y; Y may be chlorine, bromine or an acyloxy group. The term carbohydrate derivative as used herein and in the appended claims is intended to refer to a compound obtained from the carbohydrate, wherein the skeleton of the carbohydrate (i. e., the carbon chain) remains substantially intact. The term derivative is thus to be distinguished from a modification in which the original carbohydrate skeleton may be degraded or increased or otherwise changed. The term acyloxy as used herein and in the appended claims is intended to refer to an acyl group holding an oxygen.

In carrying out the present invention there may be used an alkyl, aryl, or aralkyl Grignard reagent. Among those which may be used are phenylmagnesium bromide, p-tolylmagnesium bromide, l-naphthylmagnesium bromide, 11- butylmagnesium bromide, l-propyl-magnesium bromide, benzylmagnesium chloride, and the like.

The process of the present invention is carried out in accordance with the general principles of the reaction between an alkyl, aryl, or aralkyl halide and the Grignard reagent. The Grignard reagent is prepared in known manner in dry ethyl ether. To this in suitable equipment and at about room temperature (about 25 C. to 35 C.) is then added slowly and with stirring a solution in ether or other inert solvent of the carbohydrate derivative to be used as one of the reactants. Usually.

the reaction starts at room temperature and there is soon formed a heavy precipitate. After all of the carbohydrate derivative reactant has been added, the mixture is heated under reflux conditions, as by means of a steam bath, for several hours. The mixture is then cooled and the ether decanted into water. The resultant ether layer is separated from the aqueous layer. From the ether layer is obtained a tertiary alcohol, as a by-product,

To the water layer which contains the l-R-ldesoxyglycose is added an alkaline substance. such as sodium hydroxide, to adjust the pH value to about 7.0. Thereafter the water layer is evaporated to dryness. The sirup remaining contains the 1-R-1-desoxyglycose and inorganic salts. Due to its extreme solubility in water, the l-R-l-desoxyglycose is preferably isolated from the sirup in the form Of a suitable derivative. such as the acetate. This is formed by adding to the sirup acetic anhydride and sodium acetate and treating the mixture in accordance with well known procedures for acetylation. In some instances, it may be necessary to take precautions to control the acetylation reaction in order to avoid frothing over. After the acetylation reaction is complete, the reaction mixture is cooled and poured into water to hydrolyze the excess anhydride. The addition of water usually precipitates the acetylated desoxyglycoses. The whole mixture is now subjected to extraction with a suitable solvent such as ethyl ether. Removal of the ether from the resultant ether extract leaves a solid material or sirup, which is a mixture of the alpha and beta isomers of the acetate of the desired l-R-l-desoxyglycose. The isomers are separated by fractional crystallization from a suitable solvent, such as 2-propanol. If desired the isomers may be deacetylated in known manner with sodium and methanol, leaving the alpha or beta isomer of l-R-desoxyglyc'ose.

An alternative method for isolation of the alpha and beta forms of the l-R-l-desoxyglycose derivative, in the event a solid is precipitated when water is added to decompose excess acetic anhydride, as above mentioned, consists of filtration oi" the solid. The alpha and beta isomers may then be separated from each other by fractional crystallization from a suitable solvent.

The amount of Grignard reagent required to effect the reaction involved in the present invention will depend upon the type of carbohydrate derivative used as a reactant. If, for example, a polyacylglycosyl halide or acetate is used as a reactant, the acyl groups of such reactant will also react with the Grignard reagent. In such case there must be sufiicient Grignard reagent to provide at least one molecular equivalent for each halogen atom or acylal group after the acyl groups are satisfied. The amount of Grignard reagent necessary for polyacylglycosyl halides or acetates is 2az+1 molecular equivalents, wherein .r equals the number of acyl groups. Some substituent groups may not require 2 molecular equivalents. In any case, however, it is necessary to provide sufiicient Grignard reagent so that the desired reaction may be effected, If an excess, i. e., about 3 to 5 molecular equivalents of the Grignard reagent in addition to the amount above specified are used the results are more satisfactory. There is no particular advantage, however, in using more than the above specified excess of the Grignard reagent.

The carbohydrate derivative should be at least partially, if not completely, soluble in ether, or

benzene, so as to permittherreaotion: with v the Grignard reagent.

Any vessel which'is provided with-means for refluxing, means for agitation; and m'eans for-gradual addition of a solution is suitable-for carrying out the process of the presentinvention;

The time required forthe reaction' 'to take place will depend upon the individual reactants present, but generally a total timeof 3 to' '5 hours is'satisfactory in carrying out the present'inv'ention;

As already indicated two anomers of:1-R--1-.-desoxyglycoses, i. e., both anz alpha and beta 'modification, are formed during: the process of the present invention. This is true regardless" of which isomer of the carbohydrate reactant is used. The beta isomer is usually obtained in crystalline form while the alpha isomer-is'usually obtained in sirupy. form. The 'crystalline beta isomer usually predominates. The term'anomer as used herein means'st'ereoisomers' ofsugars and sugar derivatives differing .from each. other in the spacial position of groups 'attached' to the reducing carbon atom.

Other derivatives, "such asthe' propion'atc, butyrate and the like, may -also be used 'to isolate the desired l-R-l-desoxyglycose.

Solvents other than 2- propanorwhi'ch may-be used to separate the isomers of the acetates-or likederivatives of l-R-l-desoxyglycoses-by fractional crystallization include methanol, ethanol, ethyl. acetate, and the like. 'Such solvents: mayalso be used to purify any of these compounds'further, if desired.

Deacetylation of the acetylated products leaves the l-R-l-desoxyglycose in the form one sirupor solid. The solid p'roduct maybe-purifiedwith 2-propanol, ethyl acetate, and thelike.

The following examples which are intendedas informative and typical only and not in alimit ing sense will further illustrate the invention, which is intended to be limitedonly =in-ac-cordance with the scope of theappended claims.

Example 1.Prepamtion of tetraacetyl-D- glucopyranosylbenzene. A solution of phenylmagnesium bromide was prepared-in conventional manner from 7.0 g. (0.291 mole) 'off magnesium turnings, 30.5 g. of bromobenzene, and 150 'ml. of absolute ethyl ether. A three necked fl'ask" equipped with a mercury seal and with means for agitation, for addition oisolution, and ior refluxing was used for the preparation of the-Grignard reagent and subsequent reaction thereof with a polyacylglycosyl halide. To the-above solution at room temperature'was added dropwise during a period of about 2 hours a-solution of g. of 2,3,4,6-tetraacetyl-D-glucosyl"bromide dissolved in 100 ml. of dry ether. Thereaction began within about 45 minutes after the addition of the tetraacetyl-D-glycosylbromide. Thereafter the mixture was maintained under reflux conditions and with'stirring for- 4 hours and30 minutes longer. A'strongstirring device was required to offset the heavy jprecipitate which settled during the first hour of "the reaction. After the reaction was complete, the-bulk of the absolute ether was separated from thereactionmixture by distillationand kept dry for-subsequent. use. The residue remaining was-decomposed carefully with pieces of ice, a-fter -which'25-ml; of acetic acid was added to dissolve-the suspended solid. Then ordinary ethyl ether was addedior extraction purposes and thetwo' layerswhich formed were separated.

From the etherlayer was recovered-almost a:

6; quantitative yield" of methyldiphenylcarbinol: (202 g.) :M; P; '79-.5-'80;5v C.

To the-water layerwasadded sodium hydroxide; solution until the pH value was :adjusted to '7.0; Then the water was removed by:distillationiunder diminished pressure. The sirup remaining-I con tained D-glycopyranosylbenzene; The sirup was acetylated byadding thereto 200 ml; of aceticz anhydr-ideand 5 to 10g. of sodium acetate -and heating the mixture on the steam bath ior 2 to' 3 hours, constant agitation beingmaintained. Then the' mixture was pouredinto- 300 to -500 1111. 0): coldwater. This caused the separation ofa-white solid. The whole mixture-was treatedwith ethyl" other to extract the acetylated product therefrom-.= After removal oi the ether from theextractthere remained 7.4 g. of acetylatedproduct (74 5% yield) in solid form. This wasdi'ssolved lir -I101) 2 -propanol and the solution allowed tocool. Crys talline tetraacetyl-betw D glyc0pyranosylbenzene separated readily upon cooling. The quantityobtained was 5.60 g. The 'melting. point of the product after recrystallization -f-rom 2-propanol wasfound to -be-156-.5 C. and; (al 9-in chloroform, l8.6, (conc. 2.010 g./l00 ml.-)-'-ofchloroform.

The filtrate remaining after the crystals=wereremoved was evaporated under- Vacuum-to-dryness. There was obtained 1.8 g.- of an-amber sirupa =whiohwas essentially all tetraacetyl-alpha-D- glucopyranosylbenzene. The sir-up couldnot becrystallized. Oxidation of each of the-isomerswith alkaline permanganate resulted =in-benzoicacid from each isomer. ((1) ofthe -sirupine chloroform was +39.8.

Example 2.Preparation of tetraacetyZ-D-- glucopyranosylbeneene. Phenylmagnesimmbromidewas made in dry ether-'(70ml.)'- from maginesium turnings (3.93 g., 0.1615 mole)-- and-br0mo-- benzene (17.3 ml.; 0.1650 mole) -using--a----three necked flask equipped with stirrer, mercury seal, anda reflux condenser protectedby'a calcium chloride tube. The Grignard solution was stirred underreflux for an additional 15 to minutes I after completion of the reaction. Heating was discontinued and a solution of 2,3,4;6-tetraacetyl-- alpha-D-glucosyl chloride (5.00 g; --0.0136-mole) I in'dry ether ('70 ml.) was added with stirring overthe course of an hour. The mixture was stirred under reflux for an additional four to five hours.-- The mixture was then cooled and the-ether de canted therefrom into cold water. The. gummyresidue was decomposed by the cautious-additiomv of water, and the last traces removedwith'a small '55 quantity. of acetic acid, these washings being-combined with the previous two phase systemof'etherfl and water. The two phases were shakem-well, filteredover a filter aid and separated. Theethen layer was washed with water and-the water layerwith ether, the washings being combined-with theappropriate phases.

The ether layer was dried over anhydrous sodium s'ulfateand decolorized by filtration: tlirou'glra bed "of decolorizing carbon supportedonabed of *filter aid. Removal of thesolvent at 100"C.,

finally under diminished pressure, left 11.5 grams." (slightly over the theoretical weight) of crii'd'e' methyldiph'enylcarbinol. This was recrystallized at-15' 'C-(frorna mixture of ethyl ether andpie't'r'o leum-etherto give crystals melting at '78-'79", and showing no mixed melting point depression'wi'thi an authentic sample.

*The pH" value of the water layer fromth'e reac tion -flwas adjusted to- 7.0 with sodium hydroxide 'solutionj and then concentratedto dryliess irf vacuo on the steam bath. Acetylation of the residue which contained D-glucopyranosylbenzene was accomplished by adding thereto acetic anhydride (150 ml.) and sodium acetate g.) and heating and stirring the mixture at 100 C. for 3 hours. (Care was exercised at the'start. of the acetylation to keep the vigor of the reaction under control and to avoid frothing over.) The acetylatlon mixture was then cooled, poured into about 200 ml. of cold water and stirred for several hours to hydrolyze the excess anhydride. The precipitate which formed was extracted into ether and the extract was washed with water, saturated sodium bicarbonate solution (until gas evolution ceased), and again with water. It was then dried over sodium sulfate and decolorized by filtration through a decolorizing carbon. Removal of the solvent left 4.57 g. (82%) of a mixture of alphaand beta-tetraacetyl-D-glucopyranosylbenzenes in solid form. Crystallization from the minimal quantity of 2-propanol gave 3.28 g. of the betamodification, M. P. 153-154". By concentration of the mother liquors to dryness in vacuo at 100 there was obtained 0.81 g. of an amber sirup, the alpha-isomer. This could not be crystallized. ((1) of the sirup in chloroform was found to be +39.9.

Example 3.--Preparation of p-(tetraacetyl-D- glucopyranosyl) toluene. p-Tolylmagnesium bromide was prepared in absolute ethyl ether from p-bromotoluene (56.1 g.) and magnesium (7.9 g.) To this was added over a period of 90 minutes a solution of 10.0 g. of 2,3,4,6-tetraacetyl-D-glucosyl chloride in 150 ml. of dry ethyl ether. The mixture was then heated under reflux conditions for 4 hours.

After the reaction was complete the mixture was treated as in Example 1 for the recovery of the desired products.

From the ether layer was obtained a new carbinol, di-p-tolylmethylcarbinol.

From the water layer, after evaporation and acetylation, there was obtained 8.65 g. (75%) of crude acetylated product. This was crystallized from 2-propanol. There was obtained from this 6.4 g. of crystalline p- (tetraacetyl-beta-D-gluc0- pyranosyDtoluene (after crystallization twice from 2-propanol M. P. 138.5 C. and (M in chloroform 42.8, conc. 1.122 g./100 ml. of chloroform) and 2.3 parts of p-(tetraacetyl-alpha- D-glucopyranosyDtoluene in the form of a sirup ((a) in chloroform +40.0) which could not be crystallized.

Oxidation of each isomer with alkaline permanganate resulted in 4,4'-benzophenonedicar-'- boxylic acid.

Example 4.Preparat2'on of I-(tetraacetyL-D- glucopyranosyl) naphthalene. The procedure was similar to that of Example 1. The Grignard reagent was prepared from l-bromonaphthalene. The quantities of the reactants used were:

l-Bromonaphthalene ml 53.2 Magnesium g 9.16 Tetraacetylglucosyl chloride g 10.0

There was obtained 8.1 g. (65%) of tetraacetyl-D- glucopyranosylnaphthalene in solid form. Fractionation of this from 2-propanol resulted in 5.4 g. of 1-(tetraacetyl-beta-D-glucopyranosyl)- naphthalene (after three recrystallizations from 2-propanol, M. P. 186.5-187 C. (M in chloroform +1.25, conc. 0.718 g./100 ml. of chloroform) and 2.7 parts of l-(tetraacetyl-alpha-D-glucopyranosynnaphthalene in the form of a sirup solvent was removed from the filtrate.

8 (do in chloroform +95.4) which could not be crystallized.

Example 5.-Preparation of I-(tetraacetyl-D- glucopyranosyl) butane. The procedure was similar to that of previous examples. The Grignard reagent was prepared from 9.16 g. of magnesium and 35.3 g. of n-butyl bromide in 140 ml. of dry ethyl ether. Then 10 g. of 2,3,4,6-tetraacetyl-D- glucosyl chloride in 105 ml. of dry ethyl ether was added during 45 minutes. The supplementary refluxing period was 5 hours.

There was obtained 16.5 of methyldi-n-butylcarbinol, and 6.26 g. (59.4%) of tetraacetyl-D- glucopyranosylbutane in the form of a sirup which crystallized partially on standing. The material could not be crystallized from 2-propanol so it was dissolved in a mixture of approximately equal parts of ethyl ether and hexane. The material which crystallized was identified as 1 (tetraacetyl-alpha-D-glucopyranosyl)butane. The melting point thereof after three crystallizations' from the same solvent was found to be 109- l09.5 C. and (0013 in chloroform +772". (Conc. 1.050 g./100 ml. of chloroform.)

After the alpha isomer was filtered ofi, the

The remaining sirup was identified as the beta isomer, (:1) 11 in chloroform +3.52.

Example 6.Prepa1'at2'on of Z-(tetraacetyl-D- glucopyranosyl)propane. The procedure was similar to that used in previous examples. The Grignard reagent was prepared from 54 g. of isopropyl bromide, 10.5 of magnesium in 175 ml. of absolute ethyl ether. Ten parts of tetraacetyl-D- glucosyl bromide in 150 ml. of dry ether was added to the Grignard reagent in the manner previously described. There was obtained 72 g. of methyldiisopropylcarbinol and 4.4 g. (43%) of 2- (tetraacetyl-D-glucopyranosyl)propane in the form of an oil.

Example 7 .Preparation of 1-benzyl-1-desoxy- 2,3,4,6-tetraacetyl-D-glucose. The procedure was similar to that used in previous examples. From 56.3 g. of benzylmagnesium chloride and 5 g. of

; tetraacetylglucosyl bromide, there was obtained 3.72 g. (72.5%) of l-benzyl-l-desoxy-D-glucose tetraacetate in the form of a sirup which would not crystallize.

Example 8.--Preparation of triacetyZ-D-xylopyranosylbenzene. A solution of phenylmagnesium bromide was perpared from 4.13 g. of mag nesium, 17.8 ml. of bromobenzene and ml. of absolute ethyl ether. To this was added during an hour 5 g. of 2,3,4-triacetyl-D-xylosyl chloride in 70 ml. of absolute ethyl ether. Stirring became difiicult because of gummy products. Stirring was discontinued and the mixture allowed to stand for 5 hours. It was then treated for recovcry of the desired desoxylglycose. There was ob tained 4.95 g. (86-87%) of triacetyl-D-xylopyranosylbenzene. Upon crystallization of this from Z-propanol there was obtained 3.9 g. of triacetylbeta-D-xylopyranosylbenzene (after three crystallizations from Z-propanol, M. P. 168.5-169 C., (0.)!) from chloroform 57.5, conc. 1.470 g./100 ml. of chloroform) and 0.74 g. of triacetyl-alpha- D-xylopyranosylbenzene ((00 in chloroform 23.0) in sirupy form.

Deacetylation of the triacetyl-beta-D-xylopyranosylbenzene with sodium and methanol yielded beta-D-xylopyranosylbenzene, M. P. 148- 148.5 C.

Example 9.Preparatio1z of p-triacetyl-D-xylopyranosyl) toluene. This is a duplicate of Exampie 8 except that 17.8 ml. of p-bromotoluene was used in place of the bromobenzene. There was obtained 4.9 g. (82.3%) of p-(triacetyl-D-xylopyranosyl) toluene, and 3.6 g. of p- (triacetyl-beta- D-xylopyranosyl)toluene which was crystalline. After three crystallizations from 2-propanol, it possessed these constants; M. P. 126 C.; (10D20 in chloroform -60.2 (conc. 1.230 g./1()0 ml. of chloroform). The specific rotation of the sirupy alpha anomer was 34.4.

Example 10.Prepamtion of heptaacetyZ-beta- Zactopyranosylbeneene. To the Grignard reagent prepared from 8.65 ml. of bromobenzene and 1.98 g. of magnesium in 35 ml. of absolute ethyl ether was added 3 g. of heptaacetyllactosyl chloride in 100 ml. of absolute ether. This addition was made all at once instead of slowly as in the other examples. The mixture was maintained, with agitation, under reflux conditions for 6 hours. Heptaacetyllac opyranosylbenzene was obtained in 69.4% yield (3.21 g.) The latter was crystallized from ethyl ether and then from 2- propanol. From this there was obtained 1.01 g. of heptaacetyl-beta-lactopyranosylbenzene (after three crystallizations from 2-propanol, M. P. 217 0.; (001) in chloroform 7.5, conc. 1.140 g./100 m1. of chloroform) and 0.9 g. of heptaacetylalpha-lactopyranosylbenzene in the form of a sirup in chloroform +10.7).

Example 11. Preparation of tetraacetylaZpha-D-glucopyranosylbenzene. To the Grignard reagent prepared from 4.7 g. of magnesium and 20 ml. of bromobenzene was added g. of alpha-glucose pentaacetate in 100 ml. of dry ethyl ether. After all of the alpha-glucose pentaacetate had been added the mixture was refluxed for an additional 3 hours. It was then treated in the manner described in preceding examples.

From the water layer was obtained 2.67 g. of tetraacetyl-alpha D glucopyranosylbenzene in the form of a sirup. (00 in chloroform was found to be +5.66". Oxidation of the sirup yielded benzoic acid.

We claim:

1. l-R-l-desoxyglycoses wherein R represents a radical selected from the group consisting of alkyl, aryl, and aralkyl.

2. l-R-l desoxyglucoses wherein R, represents a radical selected from the group consisting of alkyl, aryl, and aralkyl.

3. The process which comprises effecting the reaction, under substantially anhydrous conditions, between 2,3,4,6 tetraacetyl D glucosyl bromide and phenylmagnesium bromide, the amount of said phenylmagnesium bromide being at least 9 molecular equivalents with respect to the 2,3,4,6-tetraacetyl-D-glucosyl bromide; the time for effecting said reaction being about 5 hours; and the temperature for effecting said reaction not exceeding that obtained by refluxing the reaction mixture on a steam bath.

4. The process which comprises effecting the reaction, under substantially anhydrous conditions, between 2,3,4,6 tetraacetyl D glucosyl chloride and n-butylmagnesium bromide, the amount of said n-butylmagnesium bromide being at least 9 molecular equivalents with respect to the 2,3,4,6-tetraacetyl-D-glucosyl chloride; the

time for efiecting said reaction bein about 5 hours; and the temperature for effecting said reaction not exceeding that obtained by refluxing the reaction mixture on a steam bath.

5. The process which comprises effecting the reaction, under substantially anhydrous conditions, between 2,3,4-triacetyl-D-xylosyl chloride and phenylmagnesium bromide, the amount of said phenylmagnesium bromide being at least 7 molecular equivalents with respect to the 2,3,4- triacetyl-D-xylosyl chloride; the time for efiecting said reaction being about 5 hours; and the temperature for efiecting said reaction not exceeding that obtained by refluxing the reaction mixture on a steam bath.

6. The process which comprises effecting the reaction, under substantially anhydrous conditions, between a tetraacylglucose derivative and a Grignar-d reagent, said tetraacylglucose derivative being characterized in that to the carbon atom of the aldehyde function there is attached a radical selected from the group consisting of Cl, Br and acyloxy; said Grignard reagent being present in the amount of at least about 9 molecular equivalents with respect to said tetraacylglucose derivative.

7. 1-phenyl-l-desoxy-D-glucose.

8. 1-phenyl-l-desoxy-D-xylose.

9. 1-tolyl-l-desoxy-D-glucose.

10. The process of preparing l-R-l-desoxyglyooses, wherein R represents a radical selected from the group consisting of alkyl, aryl and aralkyl, which comprises effecting the reaction, under substantially anhydrous conditions, between a glycose derivative and a Grignard reagent, said glycose derivative being characterized in that the carbon atom of the aldehyde function has attached to it a substituent from the group consisting of bromine, chlorine and acyloxy and in that said glycose derivative contains protected hydroxyl'groups; the amount of said Grignard reagent being at least about 2zzz+1 molecular equivalents with respect to said glycose derivative wherein :r is equal to the number of protected hydroxyl groups.

11. The process which comprises effecting the reaction, under substantially anhydrous conditions, between a polyacylglycosyl ester and a Grignard reagent, said Grignard reagent being present in the amount of at least about 2x+1 molecular equivalents with respect to said polyacylglycosyl ester wherein a: is equal to the number of acyl groups.

12. The process according to claim: 10 wherein the time for effecting said reaction ranges from about 3 to about 5 hours.

WILLIAM ANDREW BONNER. CHARLES D. HURD.

REFERENCES CITED The following references are of record in the file of this patent:

Paal et al.: Ber., v. 39 (1906), pp. 1361, 2823, 2 pages.

Fischer et al.: Ber., v. 45 (1912), pp. 912-914, 3 pages.

Froschl et al.: Monatsh, v. 55 (1930), p. 29, 1 page. 

